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Adhesive sheet, metal-laminated sheet and printed wiring board

a technology of printed circuit board and adhesive sheet, which is applied in the direction of transportation and packaging, synthetic resin layered products, chemical instruments and processes, etc., can solve the problems inability to solve, and easy occurrence of warpage and distortion, etc., to reduce the adhesion strength of flexible metal foil laminate, the effect of suppressing the gelling of polyamic acid and small molecular weigh

Inactive Publication Date: 2009-03-05
TOYOBO CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0126]Besides this, for formation of an adhesive layer, a polyamideimide resin, a polyether imide resin, a polyester imide resin and the like can be used alone or in an appropriate combination as long as the advantage of the present invention is not impaired.
[0127]As long as the advantage of the present invention is not impaired, a thermosetting adhesive, for example, an epoxy or cyanate adhesive, may be mixed with the thermoplastic adhesive of the present invention, and the proportion of the thermosetting adhesive is 40 mass % at most relative to the total mass of the adhesive composition constituting the adhesive layer.
[0128]The aforementioned thermoplastic polyimide resin can be produced by reacting the aforementioned respective components, and further, when the case demands, other tetracarboxylic acid dianhydride and other diamine, in an organic solvent, at a temperature not more than about 100° C., particularly 20° C.-60° C., to give a polyamic acid solution, and using this polyamic acid solution as a dope solution.
[0129]In addition, a solution of a thermocompression bonding polyimide resin in an organic solvent can be obtained by affording a powder by heating a solution of polyamic acid produced as mentioned above to 150-250° C., or adding an imidating agent to allow reaction at a temperature of 150° C. or below, particularly 15-50° C., to perform imide cyclization and evaporating the solvent, or precipitation in a poor solvent, and dissolving the powder in an organic solution.
[0130]To obtain a thermoplastic polyimide resin in the present invention, respective components are preferably reacted in the aforementioned organic solvent in proportions such that the ratio of the amount of diamine used (the number of moles of amino group) to the total number of moles of acid anhydride (total mol of acid anhydride group of tetraacid dianhydride and dicarboxylic acid anhydride) is preferably 0.92-1.1, particularly 0.98-1.1, especially 0.99-1.1, and the ratio of the amount of dicarboxylic acid anhydride used to the number of moles of acid anhydride group of tetracarboxylic acid dianhydride is preferably not more than 0.05, particularly not more than 0.02.
[0131]When the proportion of the aforementioned diamine and dicarboxylic acid anhydride used is outside the aforementioned range, the obtained polyamic acid and thermoplastic polyimide obtained by imidating same have small molecular weights, which in turn decreases the adhesion strength of the flexible metal foil laminate. For the purpose of suppressing gelling of polyamic acid, a phosphorus stabilizer, for example, triphenyl phosphite, triphenyl phosphate and the like can be added within the range of 0.01-1 mass % relative to the solid (polymer) concentration during polymerization of polyamic acid. For the purpose of promoting imidation, a basic organic compound catalyst can be added to a dope solution.

Problems solved by technology

Conventionally known substrate films made of a polyimide film or a polyimide benzoxazole film are inferior in heat resistance as compared to substrates made of ceramic.
In addition, they have problem of easy occurrence of warpage and distortion during production of electronic parts due to property variation within the film.
However, even if apparent film warpage, namely, exteriorized film warpage etc., could be eliminated, the problem of potential distortion that could be exteriorized by a treatment at a high temperature to cause curling, which treatment is particularly necessary for high temperature processing for the application of electronic parts, has not been solved.
Accordingly, even if a film shows small apparent warpage, if it permits curling during processing, the yield of production decreases and high quality electronic parts are often difficult to obtain.

Method used

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  • Adhesive sheet, metal-laminated sheet and printed wiring board
  • Adhesive sheet, metal-laminated sheet and printed wiring board
  • Adhesive sheet, metal-laminated sheet and printed wiring board

Examples

Experimental program
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Effect test

examples

[0147]The present invention is explained in more detail in the following by referring to the Examples and Comparative Examples below, which are not to be construed as limitative. The evaluation method of the properties in the following Examples are as shown below, wherein the degree of curl after a heat treatment at 300° C. is based on the aforementioned method.

1. Thickness of Polyimide Film

[0148]A micrometer (Millitron® 1245D manufactured by FEINPRUF) was used for the measurement.

2. Degree of Warpage of Polyimide Film and Sheet (Apparent Degree of Warpage)

[0149]As shown in FIG. 1(C), a 50 mm×50 mm film test piece was stood still on a flat plane to form a concave, an average distance from each top point on the test piece to the flat plane (h1, h2, h3, h4: unit mm) was taken as the amount of warpage (mm), and a value shown by the percentage (%) of the amount of warpage relative to the distance (35.36 mm) from each top point on the test piece to the center was obtained.

[0150]Specifica...

production examples 1-3

[0163]A container equipped with a nitrogen inlet tube, a thermometer and a stirrer bar was substituted with nitrogen, and ODA was placed therein. Then, DMAC was added and, after complete dissolution, PMDA was added, and the mixture was polymerized by stirring at 25° C. for 5 hr at a molar ratio of ODA and PMDA as monomers of 1 / 1 in DMAC while adjusting the monomer charge concentration to 15 mass %. As a result, a brown viscous polyamic acid solution was obtained.

[0164]AA (15 parts by mass) and IQ (3 parts by mass) were added to the obtained polyamic acid solution (100 parts by mass), and the mixture was applied to the lubricant-free surface of a polyester film (COSMOSHINE®A4100, manufactured by Toyo Boseki Kabushiki Kaisha) having a thickness of 188 micron and a width of 800 mm, in a coating width of 740 mm (squeegee / belt gap 430 μm). The film was dried during passage through a continuous drying furnace having 4 drying zones. In each zone, 3 rows of slit-like air outlets were set fo...

production examples 4-6

[0181]Using PMDA and BPDA as an aromatic tetracarboxylic acid dianhydride component and ODA and P-PDA as a diamine component, the four kinds of monomers were polymerized at a molar ratio of PMDA / BPDA / ODA / P-PDA of 1 / 0.5 / 1 / 0.5 in DMF while adjusting the monomer charge concentration to 16 mass % to give a solution of polyamic acid in DMF. The obtained polyamic acid solution was applied to a stainless belt (gap between squeegee / belt 400 μm), and dried in the same manner as in Production Examples 1-3. By releasing the polyamic acid film that became self-supporting after the drying from a stainless belt, each green film having a thickness of 49.5 μm, i.e., Production Examples 4-6 were obtained. The value of |IMA−IMB| for respective GFs was 1.4, 4.2 and 4.8, respectively.

[0182]The obtained GFs were subjected to 2-step heating under the conditions of first step: 180° C., 3 min, temperature rise rate 4° C. / sec, second step: 460° C., 2 min, by passing the films through a nitrogen-substituted ...

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Abstract

The adhesive sheet contains a substrate film and an adhesive layer formed at least on one surface of the substrate film. The substrate film is made of a polyimide film showing a degree of curl after a heat treatment at 300° C. of not more than 10%. The adhesive sheet of the present invention can be used for electronic parts and the like exposed to high temperature particularly because warpage and distortion thereof caused by a high temperature treatment are suppressed, and can improve quality and yield of electronic parts and the like.

Description

REFERENCE TO RELATED APPLICATIONS[0001]This application is a national stage application under 35 USC 371 of International Application No. PCT / JP2005 / 012624, filed Jul. 1, 2005, which claims the priority of Japanese Applications Nos. 2005-122566, 2005-122567, 2005-122568 and 2005-122569, each filed on Apr. 20, 2005. The contents of the International Applications and the prior Japanese applications are herein incorporated by reference.FIELD OF THE INVENTION[0002]The present invention relates to an adhesive sheet, a metal-laminated sheet and a printed circuit board. More particularly, the present invention relates to an adhesive sheet used for forming an insulating layer for a printed circuit board and the like to be used for a flexible printed circuit substrate and the like aiming at down-sizing and reducing weight of electronic devices and electronic parts, a metal-laminated sheet wherein a metal foil is laminated on the adhesive sheet and a printed circuit board obtained by processi...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): H05K1/02B32B3/26B32B15/04
CPCB32B15/08H05K3/386Y10T428/24628H05K2201/0154H05K2201/0195H05K3/4626Y10T428/31678B32B27/34
Inventor MAEDA, SATOSHIKAWAHARA, KEIZOTSUTSUMI, MASAYUKIYOSHIDA, TAKEFUMI
Owner TOYOBO CO LTD
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